A method for producing high-quality nickel sulfamate for electroplating
By optimizing the synthesis steps and reaction conditions of nickel sulfonate, combining high-purity nickel carbonyl powder and advanced impurity removal processes, the problems of high impurity content and great environmental impact in traditional preparation methods are solved, and high-purity and efficient nickel sulfonate production are achieved to meet the needs of high-end electronic components and other fields.
Patent Information
- Application Number
- CN202411938002.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-26
- Publication Date
- 2025-04-01
AI Technical Summary
The traditional nickel sulfonate preparation method has problems such as long synthesis process, high impurity content, and a great impact on the environment of production processes, making it difficult to meet the demand for high-quality electroplating in high-end electronic components, automotive parts, aerospace and other fields.
By optimizing the synthesis steps and strictly controlling the reaction conditions, high-purity nickel carbonyl powder and advanced impurity removal processes are adopted, including multi-stage washing, precision filtration and ion exchange resin impurity removal, significantly reducing the impurity content in the product and improving the purity and electroplating performance of nickel sulfonate.
The nickel ion content in the nickel sulfamate solution is achieved by more than 180g/L, the conventional metal ions are less than 1ppm, and the sulfate content is less than 0.2g/L, achieving the requirements of high-quality nickel sulfamate, with short process flow, low energy consumption, harmless treatment of waste gas, and high metal yield.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of electroplating chemical preparation, and in particular to a method for producing high-quality nickel sulfamate for electroplating. Background Art
[0002] In the modern electroplating industry, nickel sulfamate is widely used due to its excellent deposition rate, deep plating ability and corrosion resistance. However, the traditional preparation process of nickel sulfamate is generally divided into two technical routes: (1) using nickel sulfate solution to synthesize nickel carbonate, using nickel carbonate to react with aminosulfonic acid to generate nickel sulfamate solution; (2) using nickel powder to react with aminosulfonic acid crystal solution to generate nickel sulfamate solution; the nickel carbonate synthesis method has problems such as long synthesis process flow and high content of anionic and cationic impurities such as Ca, Na, and sulfate. The nickel powder direct reaction method has raw material limitations, which are mainly manifested in extremely strict requirements on the quality of nickel powder, and there are no corresponding impurity removal measures at the back end. The quality of the output product is unstable, the impurity content is high, and the production process has a greater impact on the environment. In order to meet the demand for high-quality electroplating layers in high-end electronic components, automotive parts, aerospace and other fields, it is urgent to develop a new production method that is efficient, environmentally friendly and can produce high-purity nickel sulfamate. Summary of the invention
[0003] 1. Technical problem to be solved: In view of the defects of the traditional method for preparing nickel sulfamate, the present invention provides a method for significantly reducing the impurity content in the product and improving the purity and electroplating performance of nickel sulfamate by optimizing the synthesis steps, strictly controlling the reaction conditions and adopting advanced impurity removal technology. Specifically, the present invention optimizes the raw materials, uses high-purity carbonyl nickel powder, and cooperates with corresponding process control conditions to further reduce the content of Ca, Na, sulfate and other ions in the nickel sulfamate solution, so as to achieve a nickel ion content of more than 180 g / L in the nickel sulfamate solution, conventional metal ions are all less than 1 ppm, and the sulfate content is less than 0.2 g / L, thereby meeting the requirements of high-quality nickel sulfamate.
[0004] 2. The technical solution adopted by the present invention is as follows: A method for producing high-quality nickel sulfamate for electroplating, comprising the following steps:
[0005] (1) Raw material pretreatment: Select high-purity carbonyl nickel powder and remove impurities such as Ca ions and Na ions through multi-stage washing.
[0006] (2) Adding materials to the reactor: In a closed reactor, add the pretreated nickel raw material and aminosulfonic acid crystals at a mass ratio of 1:4, start stirring, and mix thoroughly.
[0007] (3) Reaction: Set the heating temperature to 45-55°C, set the stirring speed to 100-120r / min, start the air dilution fan, and take samples every 4 hours to detect the nickel concentration after the temperature in the kettle reaches the preset temperature.
[0008] (4) Filtration: When the nickel ion concentration of the sampled solution is greater than 180 g / L and the pH is greater than 4.0, the reaction is qualified. After the reaction is qualified, the unreacted aminosulfonic acid crystals, carbonyl nickel powder, and trace amounts of nickel sulfide and other particulate impurities are removed by precision filtration.
[0009] (5) Purification: remove ion impurities such as Fe, Cr, and Cu in the solution by ion exchange resin adsorption.
[0010] (6) Solution post-treatment: The final product is subjected to chemical composition analysis and conductivity measurement, and canned according to standard requirements to obtain the final nickel sulfamate product.
[0011] A further technical solution is that in step (1), pure water is added into the washing tank, stirring is started, and then carbonyl nickel powder is slowly added for washing.
[0012] A further technical solution is that in step (2), after adding the carbonyl nickel powder and aminosulfonic acid, ultrapure water is added, and the amount of ultrapure water added is 4 times the amount of the carbonyl nickel powder added.
[0013] A further technical solution is that in step (3), the stirring speed is adjusted to 25 r / min during the sampling process.
[0014] A further technical solution is that in step (4), the filtration accuracy of the precision filter is 0.2 microns, the precision filtration process pressure is 0.2-0.25 MPa, and the liquid inlet flow rate is 0.06-0.1 m3 / min.
[0015] A further technical solution is that in step (5), chelating resin is used for iron removal, the liquid inlet flow rate is 3-6BV / h, and the liquid inlet is circulated during the iron removal process.
[0016] A further technical solution is that in step (5), chelating resin is used for copper removal, the temperature of the copper removal solution is 40-50° C., and the liquid inlet flow rate is 2-3 BV / h.
[0017] A further technical solution is that in step (6), the nickel element is analyzed by EDTA titration, the conventional metal elements are analyzed by ICP instrumentation, and the sulfate and chloride ions are analyzed by turbidity.
[0018] 3. Due to the adoption of the above technical scheme, the beneficial effects of the present invention are as follows: the process flow of the present invention is short, the energy consumption of the production process is low, the waste gas is harmlessly treated, the waste residue is recovered and dissolved and reused in the system, the metal yield is high, and a nickel powder pretreatment process is adopted. No impurities are introduced during the production process. An advanced precision filtration system and a chelating resin impurity removal system are provided to remove particulate impurities and Cu and Fe ions, control the reaction temperature and rate, and effectively inhibit the decomposition of sulfate. The indicators of the solution produced by the above process are significantly better than those of the same industry.
[0019] The present invention can further reduce the contents of Ca, Na, sulfate and other ions in the nickel sulfamate solution by optimizing raw materials, using high-purity carbonyl nickel powder and matching corresponding process control conditions, so as to achieve a nickel ion content of more than 180 g / L in the nickel sulfamate solution, a conventional metal ion content of less than 1 ppm, and a sulfate content of less than 0.2 g / L, thereby meeting the requirements for high-quality nickel sulfamate. BRIEF DESCRIPTION OF THE DRAWINGS
[0020] Figure 1 It is a process flow chart of the present invention. DETAILED DESCRIPTION
[0021] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with embodiments.
[0022] The raw material components of the present invention are shown in the table below:
[0023] Table 1: Raw material composition table
[0024]
[0025] Embodiment 1
[0026] (1) Raw material pretreatment: Take 1 t of carbonyl nickel powder, add it into a reactor, add 4 m3 of ultrapure water, start stirring, mix evenly and stir for 1 hour, let it stand until the nickel powder is completely settled, then drain the washing water, continue to add 4 m3 of ultrapure water, start stirring and washing for 2 hours, then let it stand and completely drain the washing water.
[0027] (2) Add 4t aminosulfonic acid, add 4m3 pure water, start the air dilution fan, start stirring, set the reaction temperature to 45 degrees, set the stirring speed to 100r / min, and start the reaction.
[0028] (3) Sampling and testing the nickel concentration of the solution was 185 g / L and the pH of the solution was 4.65. Precision filtration was started, the inlet pressure was set to 0.2 MPa, and the inlet flow rate was set to 0.06 m3 / min for precision filtration.
[0029] (4) Open the liquid inlet valve of the chelating resin iron removal system, set the liquid inlet rate to 3BV, and perform ion exchange iron removal.
[0030] (5) Set the temperature of the liquid after iron removal to 40°C. After the temperature reaches the preset condition, open the liquid inlet valve of the chelating resin copper removal system, set the liquid inlet flow rate to 2BV, and perform the copper removal operation. After the copper removal is completed, transfer the solution to the pre-packaging liquid tank.
[0031] (6) Take samples to test the element indicators in the solution, and package the finished products after passing the test.
[0032] Embodiment 2
[0033] (1) Raw material pretreatment: Take 1 t of carbonyl nickel powder, add it into a reactor, add 4 m3 of ultrapure water, start stirring, mix evenly and stir for 1 hour, let it stand until the nickel powder is completely settled, then drain the washing water, continue to add 4 m3 of ultrapure water, start stirring and washing for 2 hours, then let it stand and completely drain the washing water.
[0034] (2) Add 4t aminosulfonic acid, add 4m3 pure water, start the air dilution fan, start stirring, set the reaction temperature to 50 degrees, set the stirring speed to 100r / min, and start the reaction.
[0035] (3) Sampling and testing the nickel concentration of the solution was 185 g / L and the pH of the solution was 4.36. Precision filtration was started, the inlet pressure was set to 0.2 MPa, and the inlet flow rate was set to 0.08 m3 / min for precision filtration.
[0036] (4) Open the liquid inlet valve of the chelating resin iron removal system, set the liquid inlet rate to 4BV, and perform ion exchange iron removal.
[0037] (5) Set the temperature of the liquid after iron removal to 45°C. After the temperature reaches the preset condition, open the liquid inlet valve of the chelating resin copper removal system, set the liquid inlet flow rate to 2.5BV, and perform the copper removal operation. After the copper removal is completed, transfer the solution to the pre-packaging liquid tank.
[0038] (6) Take samples to test the element indicators in the solution, and package the finished products after passing the test.
[0039] Embodiment 3
[0040] (1) Raw material pretreatment: Take 1 t of carbonyl nickel powder, add it into a reactor, add 4 m3 of ultrapure water, start stirring, mix evenly and stir for 1 hour, let it stand until the nickel powder is completely settled, then drain the washing water, continue to add 4 m3 of ultrapure water, start stirring and washing for 2 hours, then let it stand and completely drain the washing water.
[0041] (2) Add 4t aminosulfonic acid, add 4m3 pure water, start the air dilution fan, start stirring, set the reaction temperature to 50 degrees, set the stirring speed to 110r / min, and start the reaction.
[0042] (3) The nickel concentration of the sampled solution was 186 g / L and the pH of the solution was 4.55. The precision filtration was started, the inlet pressure was set to 0.25 MPa, and the inlet flow rate was set to 0.08 m3 / min for precision filtration.
[0043] (4) Open the liquid inlet valve of the chelating resin iron removal system, set the liquid inlet rate to 5BV, and perform ion exchange iron removal.
[0044] (5) Set the temperature of the liquid after iron removal to 45°C. After the temperature reaches the preset condition, open the liquid inlet valve of the chelating resin copper removal system, set the liquid inlet flow rate to 2.5BV, and perform the copper removal operation. After the copper removal is completed, transfer the solution to the pre-packaging liquid tank.
[0045] (6) Take samples to test the element indicators in the solution, and package the finished products after passing the test.
[0046] Embodiment 4
[0047] (1) Raw material pretreatment: Take 1 t of carbonyl nickel powder, add it into the reactor, add 2 m3 of ultrapure water, start stirring, mix evenly and stir for 1 hour, let it stand until the nickel powder is completely settled, then drain the washing water, continue to add 4 m3 of ultrapure water, start stirring and washing for 2 hours, then let it stand and completely drain the washing water.
[0048] (2) Add 4t aminosulfonic acid, add 4m3 pure water, start the air dilution fan, start stirring, set the reaction temperature to 55 degrees, set the stirring speed to 120r / min, and start the reaction.
[0049] (3) Sampling and testing the nickel concentration of the solution was 188 g / L and the pH of the solution was 4.45. Precision filtration was started, the inlet pressure was set to 0.25 MPa, and the inlet flow rate was set to 0.08 m3 / min for precision filtration.
[0050] (4) Open the liquid inlet valve of the chelating resin iron removal system, set the liquid inlet rate to 6BV, and perform ion exchange iron removal.
[0051] (5) Set the temperature of the liquid after iron removal to 50°C. After the temperature reaches the preset condition, open the liquid inlet valve of the chelating resin copper removal system, set the liquid inlet flow rate to 3BV, and perform the copper removal operation. After the copper removal is completed, transfer the solution to the pre-packaging liquid tank.
[0052] (6) Take samples to test the element indicators in the solution, and package the finished products after passing the test.
[0053] Embodiment 5
[0054] (1) Raw material pretreatment: Take 1 t of carbonyl nickel powder, add it into the reactor, add 2 m3 of ultrapure water, start stirring, mix evenly and stir for 1 hour, let it stand until the nickel powder is completely settled, then drain the washing water, continue to add 4 m3 of ultrapure water, start stirring and washing for 2 hours, then let it stand and completely drain the washing water.
[0055] (2) Add 4t aminosulfonic acid, add 4m3 pure water, start the air dilution fan, start stirring, set the reaction temperature to 55 degrees, set the stirring speed to 100r / min, and start the reaction.
[0056] (3) Sampling and testing the nickel concentration of the solution is 185 g / L, the solution pH is 4.45, and precision filtration is started. The liquid inlet pressure is set to 0.25 MPa and the liquid inlet flow rate is set to 0.1 m3 / min for precision filtration.
[0057] (4) Open the liquid inlet valve of the chelating resin iron removal system, set the liquid inlet rate to 5BV, and perform ion exchange iron removal.
[0058] (5) Set the temperature of the liquid after iron removal to 50°C. After the temperature reaches the preset condition, open the liquid inlet valve of the chelating resin copper removal system, set the liquid inlet flow rate to 2.5BV, and perform the copper removal operation. After the copper removal is completed, transfer the solution to the pre-packaging liquid tank.
[0059] (6) Take samples to test the element indicators in the solution, and package the finished products after passing the test.
[0060] From Examples 1-5, a 100 ml portion of product solution was randomly taken from each example, and the following performance test experiment was performed on each sample.
[0061] 1. Test product solution indicators
[0062] With reference to the detection method in GB / T23847-2017, various indicators of the sample were detected and the data were recorded, and the nickel content (g / L), iron content (mg / L), copper content (mg / L), calcium content (mg / L), chromium content (mg / L), chloride ion content (mg / L), sulfate content (mg / L) and pH value of the samples in the embodiments and comparative examples were calculated.
[0063] 2. Test results: The test results of the samples prepared in Examples 1-5 are shown in Table 2.
[0064] Table 2: Sample test results
[0065]
[0066] According to the above test results, it can be seen that the nickel sulfamate solution synthesized by the above method has a high nickel content, a stable pH value, and a low impurity content. All indicators are better than the superior standard of nickel sulfamate in the "GB / T 23847-2017" standard.
[0067] The above are only preferred embodiments of the present invention.
Claims
1. A method for producing high-quality nickel sulfamate for electroplating, characterized in that: The following steps are involved: (1) Raw material pretreatment: Select high-purity carbonyl nickel powder and remove impurities such as Ca ions and Na ions through multi-stage washing. (2) Adding materials to the reactor: In a closed reactor, add the pretreated nickel raw material and aminosulfonic acid crystals at a mass ratio of 1:4, start stirring, and mix thoroughly. (3) Reaction: Set the heating temperature to 45-55°C, set the stirring speed to 100-120r / min, start the air dilution fan, and take samples every 4 hours to detect the nickel concentration after the temperature in the kettle reaches the preset temperature. (4) Filtration: When the nickel ion concentration of the sampled solution is greater than 180 g / L and the pH is greater than 4.0, the reaction is qualified. After the reaction is qualified, the unreacted aminosulfonic acid crystals, carbonyl nickel powder and trace nickel sulfide particulate impurities are removed by precision filtration. (5) Purification: remove ion impurities such as Fe, Cr, and Cu in the solution by ion exchange resin adsorption. (6) Solution post-treatment: The final product is subjected to chemical composition analysis and conductivity measurement, and canned after meeting standard requirements to obtain the final nickel sulfamate product, wherein the nickel ion content in the nickel sulfamate solution is above 180 g / L.
2. The method for producing high-quality nickel sulfamate for electroplating according to claim 1, characterized in that: In step (1), pure water is added into the washing tank, stirring is started, and then carbonyl nickel powder is slowly added for washing.
3. The method for producing high-quality nickel sulfamate for electroplating according to claim 1, characterized in that: In step (2), after adding the carbonyl nickel powder and aminosulfonic acid, ultrapure water is added, and the amount of ultrapure water added is 4 times the amount of the carbonyl nickel powder added.
4. The method for producing high-quality nickel sulfamate for electroplating according to claim 1, characterized in that: In step (3), the stirring speed is adjusted to 25 r / min during the sampling process.
5. The method for producing high-quality nickel sulfamate for electroplating according to claim 1, characterized in that: In step (4), the filtration accuracy of the precision filter is 0.2 microns, the precision filtration process pressure is 0.2-0.25 MPa, and the liquid inlet flow rate is 0.06-0.1 m³ / min.
6. The method for producing high-quality nickel sulfamate for electroplating according to claim 1, characterized in that: In step (5), chelating resin is used for iron removal, the liquid inlet flow rate is 3-6BV / h, and the liquid inlet is circulated during the iron removal process.
7. The method for producing high-quality nickel sulfamate for electroplating according to claim 1, characterized in that: In step (5), chelating resin is used for copper removal, the temperature of the copper removal solution is 40-50°C, and the liquid flow rate is 2-3BV / h.
8. The method for producing high-quality nickel sulfamate for electroplating according to claim 1, characterized in that: In step (6), the nickel element is analyzed by EDTA titration, the conventional metal elements are analyzed by ICP instrumentation, and the sulfate and chloride ions are analyzed by turbidity.